Process for treating cellulosic textile material with triacryl-s-triazines



, and/ or alcohol.

of the cellulose fibers whereby the properties of wrinkle 3,016,28l PROCESS FOR TREATING CELLULOSIC TEXTILE MATERIAL WITH TRIACRYLYL-s-TRIAZINES Edward L. Kropa, Greensboro, N.C., and Arthur S.

Nyquist, Darien, Conn., assignors to American Cyanamid Company, New York, N.Y., a corporation of Maine N Drawing. Filed Oct. 16-, 1957, Ser. No. 690,454

Claims. (Cl. 85-1162) The present invention relatesto a process for treating cellulosic textile materials to impart dimensional stability and wrinkle resistance thereto and to the textile materials so treated.

- The impartation of dimensional stability and wrinkle resistance to textile fabrics heretofore has been accomplished by employing a wide variety of finishing agents and techniques. Most frequently, these properties are imparted to cellulosic textile fabric by applying thermojsetting 'aminoplast resins, as for example, melamineformaldehyde resins, urea-formaldehyde resins, including ethylene urea-formaldehyde resins, and their various alkylated derivatives, and curing the same in the presence of an acid curing catalyst. These di or-multi-functional materials usually impart the properties of dimensional stability and Wrinkle resistance to the textile material through the reaction between the labile hydrogens of the cellulosic hydroxyl'group and the hydroxyl or alkoxy group of the aminoplast resin, with the splitting of water These reactions result in cross-linking resistance and shrinkage control are accomplished.

For the most part, these-finishing operations are highly satisfactory and do impart excellent wrinkle resistance and dimensional stability to the fabric so treated. 'They do, however, suffer certain shortcomings, principal among which is the deleterious effect imparted to fabric so finished by chlorine absorption, as when the fabric is washed in a media containing chlorine bleach; These effects manifest themselves as discoloration of the treated fabric or by adversely affecting the tensile strength of the treated fabric when it is scorched subsequent to chlorine bleaching. Y Thermoplastic polymeric materials have been employed in the treatment of cellulosic textiles, as for example,

binders for non-woven fabric, for the impartation of special hand eifects, as for example, stiffness, either .alone or in combination with other finishing-materials,

such as the aminoplast resins enumerated above. These thermoplastic textile finishes do not cross-link the cellulose fiber to impart dimensional stability and wrinkle resistance, in that their chemical structure restricts such activity. Any effect that finishes of this-type impart to textile materials, such as wrinkle resistance and shrinkage control, appears to be the result of a' purely physical association. i 1

It is an object of the present invention to provide a process for'the treatment of cellulosic textile materials to impart dimensional stability thereto and wrinkle resistance through the cross-linking of the cellulosefibers with a specific classof polyfunctional compound.

It is afurther object of the present invention to provide cellulosic textile materials having improved dimensional stability and wrinkle resistance prepared in accordance with such a process.

These and other objects and advantages of thepresent invention will become apparent from the detailed description set forth hereinbelow. Y

According to ,the present invention, a process is provided for treating cellulosic textile materials to impart shrinkage control and wrinkle resistance thereto through crosslinking of the cellulosic fibers, .which comprises Patented Jan. 9, 1962 wherein R R and. R are members selected from the group consisting of hydrogen, methyl, ethyl, propyl and butyl. Also. included in the treating mixture or blend is an inert solvent for the triazine compound,vwhen the latter is not a water-soluble bisulfite-modifiedadduct. The alkaline compound employed as'catalyst is present in, an amount sufiicient tocatalyze the reaction between the cellulosic. textile material and the treating compound. Thereafter, the fabric is dried and cured.

. By cellulosic textile materia as the term is used herein, it is meant fibers, films, filaments, formed fabrics, woven and non-woven, felted, or otherwise classified textile materials composed of at least 50% of cellulosic materials, which term is intended to include cotton, viscose rayon, jute, hemp, sisal, and the like, and mixtures thereof. For practical purposes, most applications are limited to formed textile materials or fabric, either woven or non-woven, composed of cotton or viscose rayon and thus for the most part the application of the present invention is directed to such fabrics.

The triazine compounds employable in the present in- 'vention may be termed l,3,5-triacrylyl-hexahydro-s-' or mixtures thereof are preferred and most efficiently employed.

The triazines coming within the general formula set forth hereinabove and which are contemplated by the present invention may be symmetrical or unsymmetrical.

Thus, where R R and R are the same, the compound may be considered symmetrical andswhere'they arekiifferent, the compounds may be considered unsymmetrical.

The .following are illustrative of symmetrical compounds! l,3,S-triacrylyl-hexahydro-s-triazine; v1,3,5-tr is1- I (Z-methy-lacrylyl)-hexahydro-s-triazine; v1,3,5-Jtris-(2-e thylacrylyl) hexahydro-s-triazine; 1,3 ,S-tri's- 2-propylacrylyl)-.hexahydro-s-triazine; 1,3,5-tris- (2 -.isopropylacr?y1yl hexahydroes-triazine; 1,3,5-tris-(2-butylacryly1) -vhexahydro-s-triazine; and 1 ,3 ,5 -tris- 2-isobutylacrylyl) .-hexahy- As illustrative .of the unsymmetrical triazines, l-acrylyl-3,5-bis-(2-ethy1acrylyl) hexahydro-striazine and l-(Z-butylacrylyl)-3,5-bis-(2 ethylacrylyl)- hexahydro-s-t'riazine may be employed. .These compounds are applied to the cellulose textile in amounts from between 3 and 25% and preferably from between 5 .and:l5%, based, on the dry weight of the textile fabric.

These triazines may be employed singly or in combination with one another in accordance with the present invention. I g

The aqueous solution of alkaline compounds employed as catalysts in the present process may be sodium hydroxide, potassium hydroxide or lithium hydroxide, sodium carbonate, sodium bicarbonate, choline, morpholine, triethanolamine, or any combination thereof. It is essential to the present process that a moderate to strong alkali catalyst material be employed, in order to effect the desired results, and that it be present in an amount sufficient to eatalyze the reaction between the cellulose and the triazine. It has been determined that the treating composition should have a pH above 8 and preferably above 9, depending upon the nature of the alkaline catalyst compound employed.

When the water-insoluble triazines are employed, a solvent must be used therewith. Such a solvent must function both as a solvent for said triazine and must further be inert with respect thereto and the treating medium. As suitable classes of solvents, broadly ethers and ketones may be mentioned. Specifically, methyl ethyl ketone and acetone may be cited by way of example, and dioxane is the preferred solvent in the present process. Other solvents which may be employed are dimethyl formamide, ethylene carbonate, and the like. These solvents and their equivalents may be employed singly or in combination with one another.

With certain of the solvents, as for example, acetone, the triazines of the present invention are not fully soluble therein. The use of strong alkaline compounds such as sodium hydroxide in such treating compositions, in addition to functioning as a catalyst for the reaction between the cellulose and triazines, functions as a solubilizing agent, rendering the triazine fully soluble in the acetone.

In accordance with the present invention, the triazine is preferably dissolved in the solvent, as for example, dioxane, and the alkaline compound employed as catalyst, as for example, sodium hydroxide, is dissolved in water. The respective solutions are then blended and the textile material treated therewith.

As has been previously pointed out, the treating composition or mixture should have an alkaline pH above 8, but preferably is above 9. It may generally be said that the pH value of the treating mixture is not significant, ex-

cept insofar as it is a measure of the necessary amount of alkaline compound present as catalyst for the reaction between the cellulose and the triazine. Thus, where the amount of catalyst present is sufiicient to provide a treating composition with a pH above 8, and preferably above 9, the presence of sufiicient catalyst is indicated. Expressed as percent of the total treating composition, the alkaline compound present as catalyst should be present in an amount of less than of the total weight of treating composition and preferably from between about 0.05-4% thereof. Based on the weight of the triazine, an amount of from bet em 5 and 15% should normally be employed. If the amount of catalyst is insufiicient to produce such pH values, the reaction proceeds too slowly and undesirable side reactions have been known to occur. If toomuch alkali is present, undesirable effects such as discoloration of the treating'textile material upon drying and curing are incurred.

The composition of the present invention may be applied by any of the conventional textile finishing techniques, as for example, padding, spraying, immersion, and the like. The process of the present invention preferably employs padding techniques.

The mixture of the present invention is applied as by padding to the cellulose textile material so as to impart from between about 3 and about 25% and preferably from between about 5 and 15% of the trazine to the textile fabric, based on the dry weight of the fabric. Thereafter, the fabric is dried and cured. For the most part, the times and temperatures of drying and curing are readily determinable. and curing is inversely proportioned to the temperatures employed. Thus, by way of example, drying and curing Generally speaking, the time of drying may be accomplished by drying the treated fabric, as for example, at 200 F. until dry to the touch, followed by curing for from 3 minutes at 290 F. to 0.5 minute at 450 F. If it is preferred to dry and cure in a single operation, times and temperatures of from 8 minutes at 250 F. to 1 minute at 450 F. may be employed.

In order that the present invention may be more fully understood, the following'examples are given primarily by way of illustration. No details found therein should be construed as limitations on the present invention, except as they appear in the appended claims. All parts and percentages are by weight unless otherwise indicated.

EXAMPLE 1 Fifteen parts of l,3,5-triacrylyl-hexahydro-s-triazine are dissolved in 150 parts of dioxane. Blended with this solution is an aqueous solution of 1.5 parts of 100% sodium hydroxide in parts of water. The pH of the blend was above 9.

80" x 80 cotton percale was padded through the solution so as to apply a wet pick-up. Thereafter, the treated fabric was dried and cured in a single operation for 6 minutes at 290 F. The amount of triazine applied to the cloth was about 6%, based on the dry weight of the fabric.

The results of this application will be reported in Table I set forth hereinbelow.

EXAMPLE 2 Twenty-five parts of l,3,5-tris-'(Z-methylacrylyl)-hexahydro-s-triazine were dissolved in parts of acetone. Blended with this solution was 2 parts of 100% potassium hydroxide in 90 parts of water. In this mixture, the po- Table 1 Dried Wrinkle Shrinkage (1 Recovery Application wash), percent (both warp and fill), de-

grees Example 1 1.1 223 Example 2 1.0 235 Control (untreated fabric) 5. 6 145 The above results clearly indicate that the application of the triazines according to the process of the present invention results in the improvement of the dimensional stability and in the wrinkle recovery of the treated fabric. In addition, in both Examples 1 and 2, the treated fabrics had a soft hand and were not stiff, indicating that the triazine did not polymerize on the surface, but cross-linked withinvthe cellulose fibers. Further, the treated fabric did not discolor as a result of chlorine absorption.

In the above table and subsequently in the present specification, the wash for the treated cotton fabric and control fabric involves washing the fabric for one hour in 0.1% soap and 0.1% soda ash at F. in an agitator Washer, followed by a thorough rinsing in water at 160 F. Shrinkage control, the measure of dimensional stability imparted, was determined by measuring the treated samples before and after washing and drying and expressing the changein dimensions as a percentage of the original dimensions.

Wrinkle recovery was determined by the use of a sarito crease-angle tester.

viVIonsanto crease-angle recovery tester, and the values EXAMPLE 3 To a solution consisting of 10 parts of 1,3,5-triacrylylhexahydro-s-triazine in $100 parts of dioxane a solution of 1 part of 100% sodium hydroxide in 60 parts of water is added followed by blending. The composition has a pH above 9.

This composition is applied to rayon challis by immersion of the challis in the treating composition for from 2 to 3 minutes. The treated fabric is then padded and pinned to size. The wet'pick-up of the treating solution is about 100%. The treated challis is air dried for about 1 /2 hours and then dried and cured for 6 minutes at Thereafter, the treated challis and an untreated control were washed in 0.1% soap at 100 F. in an agitator Washenfollowed by thorough rinsing in water at 100 F. and each of the samples were measured for shrinkage control in accordance with the procedure outlined hereini The treated: fabric underwent shrinkage of 8% and the untreated sample had-a shrinkage of about 19%, thus indicati'nig that the treatment of rayon challis according to the present invention results in a positive and substantial improvement in shrinkage control.

In U.S. Patent No; 2,559,694 (which patent is incorporated by reference herein) it is disclosed that compounds of the type generally contemplated for use in the present invention have heretofore been used in conjunction with textile materials. Thus, for example, it is broadly disclosed that 1,3,5triacrylyl-hexahydro-s-triazine may be polymerized in the presence of textile materials. In this contemplated reaction, the t-riazine. is polymerized in the presence of the textile material through the initiating action of "a catalyst for the polymerization, as

Such a treatment does not impart dimensional stability and wrinkle resistance through across-linking of the fibers of the textile material, but'alternatively results in a.

said patent. Three applications were then made M80" x 80" cotton percale as follows:

(a) solids of the bisulfite adduct was boiled with hydrogen peroxide in water for 10' minutes and then applied to the cotton percale, followed by drying and curing in accordance with the procedure set forth in Example 6 .of the said patent. 1 (b) The same procedure as in (a) above was followed except that the step of boiling the bisulfite adductpreliminary to application to the percale was omitted.

(c) l0%-solicls of the bisulfite adductcontaining 10% NaOH based onthe adduct solids was applied to the percale, and the cloth was dried 2 minutes at 225 F. and

The treated fabric and untreated control were then tested, for wrinkle recovery, hand 'andstiifnes's. The results are recorded in Tablell hereinbelow. The wrinkle recovery values areindegrees', as determined-by a Monand d'e'terminedby a skilled operator actually feeling the "fabric. The stitfness values reported ar'eobtained by employing a Gurley stiffness tester, and the values reported are in milligrams and represent total Warp plus filling. The higher the value, the stiffer the fabric.

The hand 'values are relative Table. II

. I Wrinkle Application Hand Gurley Recovery .Stifiness (Total W I 144 150 v 144 c 206 Untreated 150 From=this data the following conclusions may be arrived at: p

(1) Polymerizationof the bisulfite adduct of 1,3,5-triacrylyl-hexahydro-s-triazine prior to application to the cotton percale effects-a mendurable increase in" fabric t stiffnessj From this it may be concluded that the resin for example, of benzo'yl peroxide or hydrogen peroxide.

is on the fabric as a coating and probably not chemically bound thereto. I

(2) The in situ polymerization of the bisulfite adduct does not occur unless the pre-polymerization step is carried out. This is evidenced by the fact that no hand modification of the fabric treated as in (b) was encountered. Thus, if the adduct polymerized to form a coating it would have rendered the fabric stiff. It should also be noted that the procedure of (b) apparently did not react orcross-link with the fabric in that no improvement in wrinkle recovery was recorded.

(3) Application of the unpolymerized bisulfiteiadduct with a catalyst employable in the process of the present invention improves substantially the wrinkle recovery of the treated fabric, and does not significantly stiffen the hand ofthe fabric. This may be interpreted to mean that in accordance with-the process of the present invention the cellulose fibers are cross-linked.

In a particular disclosed application according to the above-cited reference, 1,3,5 -triacrylyl-hexahydro s-triazine is rendered water soluble by modification with a sulfite group and is'then polymerized in the presence of'percale through the initiating activity of a hydrogen peroxide Since the triazines of the present invention are em- .ployed as monomers or lower order polymers, and since the finished fabric has dimensional stability, wrinkle resistance and a soft hand, it is believed that a major por tion of the triazine enters into the cellulose fiber to crosslink the same 'It is believed that the reaction maybe r epresented.as follows: I

As has been pointed out hereinabove, the present proc-. ess is directed primafily to the improvement of dimensional stability and wrinkle resistance of cellulosic fabrics.

- While the present process effects reaction with cellulosic textile materials of the type contemplated and de- --scribed hereinabove, these materials may, of course, be mixedwith other non-cellulosic materials. Thus, for example, the cellulosic textileumaterial may be; blended nylon, polyester fibers, acrylic'fibers, and other syn- 'rial basedon its dry weight.

Where compatible, the treating composition of the present invention may be employed with pigments, dyes, lubricants, wetting agents and the like, and to some extent other finishing resinous materials, as for example, aminotriazine-formaldehyde resins such as melamine-formaldehyde resins, ethylene urea-formaldehyde resins, ureaformaldehyde resins and the alkylated derivatives thereof.

We claim:

1. A processfor treating cellulosic textile material to impart shrinkage control and wrinkle resistance thereto through cross-linking of the cellulosic fibers, which consists essentially in treating said textile material in its entirety with a composition comprising an aqueous solution of an alkaline compound as a catalyst and a triazine compound selected from the group consisting of those having the following general formula: 7

wherein R R and R are selected from the group consisting of hydrogen, methyl, ethyl, propyl, butyl and the water-soluble bisulfite-modified adducts thereof, said alkaline catalyst being present in an amount sufficient to catalyze a reaction between the cellulose and said compound, and thereafter drying and curing the treated fabric.

2. A process for treating cellulosic textile material to impart shrinkage control and wrinkle resistance thereto through cross-linking of the cellulosic fibers, which consists essentially in treating said textile material in its entirety with a composition comprising an aqueous solution of an alkaline compound as catalyst and a solvent solution of a triazine having the following general formula:

wherein R R and R are selected from the group consisting of hydrogen, methyl, ethyl, propyl and butyl, said solvent being inert with respect to said triazine, said alkaline catalyst being present in an amount sufiicient to catalyze a reaction between the cellulosic material and said compound said compound being appliedso as to impart from between 3 and 25% by weight thereof to the material, based on the weight of the material, and thereafter rying and curing the treated fabric.

3. A process according to claim 2 in which the alkaline catalyst is sodium hydroxide, R -R are hydrogen, and thesolvent for the triazine is dioxane.

4. A process according to claim 2 in'which R --R are methyl.

5. A process according to claim 2 in which R -R are ethyl.

6. A process according to claim 2 in which the cellulosic material is cotton.

7. A process according-to claim 2 in which from between 5 and 15% of the. triazine is applied to the mate- 8. A process for treating cellulosic textile material to impart shrinkage control and wrinkle resistance thereto 'soluble bisulfite adduct of a triazine having the following general formula:

wherein R R and R are selected from the group consisting of hydrogen, methyl, ethyl, propyl and butyl, said alkali metal hydroxide catalyst being present in an amount suflicient to catalyze a reaction between the cellulosic material and said compound said compound being applied so as to impart from between 3 to 25% by weight thereof to the material, based on the weight of the material, and thereafter drying and curing the treated fabric.

9. Cellulosic textile material having improved shrinkage control and wrinkle resistance through cross-linking of the cellulosic fibers with a compound selected from the group consisting of those having the following general formula:

and the bisulfite-modified adducts thereof, in which R, R and R are selected from the group consisting of hydrogen, methyl, ethyl, propyl and butyl.

10. Cellulosic textile material having improved shrinkage control and wrinkle resistance through cross-linking of the cellulosic fibers with from between 3 and 25 of a compound selected from the group consisting of those having the following general formula:

and the bisulfite-modified adducts thereof, in which R R and R are selected from the group consisting of hydrogen, methyl, ethyl, propyl and butyl.

References Cited inthe file of this patent UNITED STATES PATENTS,

1,886,480 Haller et al. Nov. 8, 1932 2,301,509 Bock et al. Nov. 10, 1942 2,332,047 'Bock et al. Oct. 19, 1943 2,559,694 Zerner 'et a1 July 10, 1951 -2,559,835 Zerner et a1 July 10, 1951 2,568,620 Gresham et al. Sept. 18, 1951 2,643,958 Kleiner et al. June 30, 1953 2,651,631

Zerner et nearest-ff. t 8f Patent No. 3 ,0 l6 281 January 9, 1962 Edward L. Kropa et a1.

It is hereby certifie ent requiring correction a corrected below.

Column 6.-

shown below instead of as. in

column 8, line 22 f0 Signed and seale (SEAL) Attest:

ERNEST W. sWIDER Attesting Officer lines 59 to 63. the formula shoul he above numbered patd that error appears in t should read as nd that the said Letters Patent (I appear as the; patent:

r "110% second occurrence, read and d this 12th day of June 1962.

DAVID L. LADD Commissioner of Patents. 

1. A PROCESS FOR TREATING CELLULOSIC TEXTILE MATERIAL TO IMPART SHRINKAGE CONTROL AND WRINKLE RESISTANCE THERETO THROUGH CROSS-LINKING IF THE CELLULOSIC FIBERS, WHICH CONSISTS ESSENTIALLY IN TREATING SAID TEXTILE MATERIAL IN ITS ENTIRETY WITH A COMPOSITION COMPRISING AN AQUEOUS SOLUTION OF AN ALKALINE COMPOUND AS A CATALYST AND A TRAIAZINE COMPOUND SELECTED FROM THE CONSISTING OF THOSE HAVING THE FOLLOWING GENERAL FORMULA: 